Rapid processing of photographic color materials



United States Patent Office 3,168,460 Patented Feb. 2, 1965 3,168,400 RAPID PROCESSING OF PHGTOGRAPHIC COLOR MATERIALS John Blackmer and Howard W. Vogt, both of Rochester,

N.Y., assignors to Eastman Kodak Company, Rochester, N.Y., a corporation of New Jersey No Drawing. Filed May 22., 1961, Ser. No. 111,489 12 Claims. (Cl. 9622) This invention relates to photography, and more particularly, a method for increasing'the speed of processing photographic films and papers for recording photographic images in color.

In multi-layer photographic elements used for color photography, there are usually at least three selectively sensitive emulsion layers coated on one side of a photo graphic support, such as film or paper.. One of the silver halide emulsions is usually selectively sensitized to the red region of the spectrum, another to the green and the third to the blue region of the spectrum. In color materials' for reversal processing, there is usually a yellow filter layer between the support and the conventional uppermost blue-sensitive layer. The redand green-sensitive layers generally lie between the yellow filter layer and the support. for processing in photographic developers containing a color coupler or color-forming compound, which couples with the oxidation products of the color developer to provide the desired color image. Other photographic ma terials are designed in such a fashion that the coupler is incorporated in the silver halide emulsion layer itself, or in alayer contiguous thereto. Such modifications are well known to those skilled in the art, and it is to be understood that the presentinvention is concerned both with photographic elements which are designed to be processed in color delevopers containing the couplers or color materials which contain the couplers in the silver halide emulsions, or in layers contiguous thereto. Multi-layer materials of the type which can be employed in the present invention have been previously described in the prior art, such as Jelley and Vittum US. Patent 2,322,027, issued June 15, 1943, and Mannes et al. US. Patent 2,252,- 718, issued August 19, 1941.

It is known that photographic silver halide emulsions can be. processed at elevated temperatures, thereby materially shortening the processing time. However, as the temperature of the processing solutions is raised, the photographic layers conventionally used suffer the serious disadvantage of softening, which causes offsetting of the layers and reticulation from the supporting surface,'such as film or paper. Attempts have been made to overcome this softening difliculty by treatment of the photographic element prior to processing with an aqueous solution containing a hardener for the conventional hydrophilic colloid layers which generally contain gelatin or some similar material. Aldehydes, such as formaldehyde, glyoxal,

succinaldehyde, glutaraldhyde, etc., have been proposed for this purpose, but it has been found that evensrnall amounts of these aldehydes will carry through. into one or more-of the color developers and react with the color,

couplers, thuscausing serious ditiiculties;

We have now found a 'novel method which permits high temperature processing'by-use-of a prebath containing a hardening agentfor the hydrophilic colloid and at the same time avoids the substantial difliculties, previously experienced by carrythrough of the hardening agent of one of the subsequent processing baths, such as the color developer, where the hardening agent has deleterious side reactions leading to'the formation of sludge and scum. According'to our process, the aforementioned difiiculties are avoided by using an aqueous bath, after the hardening bath, which contains an amine which reacts with the re- Such color materials may be designed sidual hardening agent, such as aldehyde, thereby preventing carrythrough into one of the subsequent treating baths. Using this technique, it has been found possible to shorten the processing time of a conventional incorporated coupler film from approximately 52. minutes by.

conventional processing, to about 19'minutes, while providing quality substantially equal to that obtainable using prolonged processing conditions.

- The prebaths used in our invention following the aldehyde hardening bath comprise an aqueous solution containing'at least one primary amine compound containing in addition to the -NH group a hydroxyl group, a carbonyl group, or an amino group, which may have a substituent thereon. The concentration of the amine co. pound in the prebath can be varied, depending upon the amount of aldehyde which carries over from the aldehyde hardening bath. In general, we have found that from about 1 gram to about 100 grams per liter-of amine compound is sufiicient to remove substantially all traces of aldehyde from the emulsion layers, so that aldehyde is not released into one of the subsequent processing baths.

( I-hN-OH Hydroxylamine HzNNH NHz Semicarbaztde H2N H2 Hydrazine HzNNH & NHNH:

Carbohydrazlde H N C NH C N H2 Biuret I (a l NH tice to dissolve one of the amine compounds in water,

and then adjust the pH of the treating solution so that a pH within the range of about 4.5 toabout 8.0 is obtained. Improved reaction of the'amine compound with the aldehyde contaminants in the emulsion layers generally occurs more rapidly at a pH below 8.0. Higher pH levels canlsometimes be used, although prolonged contact times maybe required in order to compensate for the lower rate of reaction.

The most advantageous concentrationoff arnine compound for a particular processing run can be" determined by developing a series" of test strips of photographic multi-layer elements wherein the" concentration of the amine compound, as well as the concentration of the Amine compounds which can be usefully employed varied by variation of the pH as mentioned above.

vantageously, the pH can bevaried by the addition of aldehyde in the hardening bath, are varied. The rate of reactivity of the amine-containing composition can be elements processed according to our invention can contain any of the conventional silver halides as the photosensitive material, and it is to be understood that our invention is not concerned with the chemical nature of these ingredients. Silver halide emulsions, such as silver chloride, silverbromoiodide, etc., can be usefully employed, although other silver halide emulsions can be employed to equal'advantage. Any of the conventional photographic supports can be used to'serve as a carrier for the silver halide films. lass, celluloseester film, etc., can be employed. 7

The concentration of aldehyde in the aldehyde hardening bath can be varied,.depending upon the processing temperature and the like. Sufiicient aldehyde is generally employed to prevent any substantial softening at hydrophiliccolloid, such as gelatin or polyvinyl alcohol.

The process of our invention can be used in'the treatment of photographic color elements designed for reversal color processing, or in the processing of negative 7 7.4 7 Example- A three-color silver bromoiodide film, wherein gelatin Was employed as the hydrophilic colloid and wherein cyan, magenta and yellow color formers of the type described in the Jelley and Vittum patent mentioned above were incorporated in the emulsions, was exposed for X second to a 500-watt tungsten lamp, adjusted to g a color temperature of 6l00 K. in an intensity scale sensitometer- The exposed strip Was then treated for .2 minutes in a hardening bath at 100 Fkhaving the following composition:

color materials, or color print materials. The important feature of our invention isthe'use of an aqueous solution containing an amine compound of the above type after treatment of thephotographic element with and over 'of any aldehyde compound into one of the sub' sequent treating baths where its presence might cause deleterious effects. Washing. with water following an aldehyde hardening bath ,does not remove sufficient aldehydeto prevent the difficulties which have been mentioned above/However, sirnple, treatment with an aqueous solution of one 'oftlie amine compounds ofjour invention removes the aldehyde and even reduces the number of Washing steps with water which have been previously employed in commercial processing or many photographic elements. compound is relatively high so. thatsome' of this compound carries over into one of the subsequent treating baths, this does not cause any serious difiiculties. It has been 'found that many of these compounds have useful properties even in' the subsequent treatingbaths. For eXample,'where grams per litervof' succinaldehyde V were employed in a hardening bath to permit high temperature processing, it was "found that the 'useful concentration of hydroxylaminetor a. salt thereof) should prebath, the element can thereafter be processed in a" If the concentration of amine I V Grams A Succinaldehyde 10 Sodium acetate 10 7 Water to make 1 liter. I

' bath having the following composition: 20

V I Grams Sodium hexametaphosphate 0.5 I-Iydroxylamine Sodium bromide u 1.0

' Sodium sulfate 50 7 Water to make 1 liter.

The treated film was then developed for 3 minutes at 100 Ffiir a black-and-white negative developer, such as one having the following composition:

Water, 90 F. (32 1iter 1.0 Sodium hexametaphosphate "grams" 2.0 .N-methyl-p-aminophenol sulfate do- 6.0 1

Sodium sulfite, desiccated; do 50.0 Hydroquinone do 60 Sodium carbonate, monohydrate 'do 35.0 Potassum bromide -Q do 2.0 Sodium. thiocyanate do 1.5 6.5% solution of 6-nitrobenzimidazole nitrate ccs.' 12.0 0.1% solution 'of potassium iodide ccs, 10.0

At this point it was possible to omit the conventional water wash and first-hardener treatment and to proceed *iwithtreatment for seconds iu an acid rinse bath having the following formula.

Acid rinse:

' :Water ml 800 Glacial acetic'acid ml 30.0 .Sodium hydroxide g 1.75 Water to liter 1 pH at 80". F. 3.8i.40

The film-was then washed for SOsecQndS in water at 100 F. and then-given either a flash exposure to strong Serial No. 699,478, filed November 29, l9-57, nowU.S.

normal sequence using conventional processing solutions and techniques, or in other cases, the'process can be.

adapted to other processing techniques, such; as surface- 'layer processing of the type described in the copending, application of Turnerand Wilson, 'Seri al lSlo. 87,874,

filed February 8', 1961.

'The following example will serve; tofillustrate the. simple techinque'of avoiding .the difliculties previously 7 experienced in processing I hardened/photographic eleme'nts'at elevatedtemperatur'es.

Patent 2,984,567; issued May-16; 1961.) The film was I then developed for 3 minutes at ,F; in a colorfdeveloper having the following formula:

. smu

rinse bath of the type illustrated above.

V ample.

At this point it was possible to omit the conventional water wash and second hardener treatments. The film was then treated for 30 seconds at 100 F. in an acid The film was then washed for 1 minute in water at 100 F. and then treated for 90 seconds at 100 F. in a bleach bath having the following composition: 7

Grams Sodium ferricyanide 60.0 Sodium hypophosphate-H O 17.6 Sodium bromide I 15.0 Sodium hydroxide 3.5 Sodium thiocyanate 5.0

Water to 1 liter.

The film was treated for 1 minute in a fixing bath having the following composition:

Water 80 F. (27 C.) i 1iter 1.0

Sodium thiosulfate grams 95.6 Sodium bisulfite do 20.0

The film was then washed for 1 minute in 100 F. water and treated for 30 seconds in a stabilizing bath having the following composition.

Constituent: Fresh tank mix Water ml 800 Formalin (37.5% formaldehyde solution) ml 4.0

operation, considerably less dirt and suspended matter were picked up from other solutions, thus making it unnecessary to use as-many wash baths as would ordinarily be employed in the processing of an unhardened film. Also, since the use of a hardened material made possible processing at a much higher temperature than normal, the hydrophilic colloid layers had much less tendency to swell in the processing solutions and made it possible to dry'andfilm in'about /3 the normal time. The processing time was only about 19 /2 minutes as compared with conventional 75 F. processing which consumed about 52 /2 minutes.

Other amine compounds can be advantageously used to obtain the unique elfects illustrated in the above ex- For instance, instead of using hydroxylamine to remove substantially all aldehyde from photographic material hardened in an aldehyde bath, carbohydrazide can be used to equal advantage. A typical formula which has been found useful for this purpose is as follows:

Carbohydrazide grams 5 Sodium sulfate do 100 Water to make liter 1 pH at 80 F. 6.0

plers, can be employed. Especially useful 'color developing agents which can be employed'inour invention include aromatic primary amines containing an amino (substituted or not) or hydroxyl substituent. The phenylenediamines and substituted derivatives thereof containing a primary amino group have been found to provide excellent results in our invention. Typical of such color-forming developers are the sulfoneamidosubstituted p-phenylenediamines disclosed'in Weissberger U.S. Patent 2,548,574, issued April 10, 1951, the substituted p-phenylenediamines disclosed in Weissberger et al. US. Patent 2,566,271, issued August 28, 1951.

In the practice of the present invention, any of the conventional couplers as described in the prior art can be used. Couplers which are particularly useful in color developers include Couplers 1-64 listed incolumn 3-5 of Spath U.S. Patent 2,956,876, issued October 18, 1960, and also the couplers as described in the same patent in column 5 as Couplers 6577 in which the couplers are included in the photographic silver halide emulsion layers are equally useful. Other couplers suitable for use in the emulsions of this invention include those described in Spence and Carroll U.S. Patent 2,640,776, issued June 2, 1953; Weissberger et al. U.S. Patent 2,407,210, issued September 3, 1946, and Weissberger et al. U.S. Patent 2,474,293, issued June 28, 1949. Other couplers 'which 'can be used in the emulsions of the present invention -Letters Patent of the United States is:

1. A process for forming a stable image in-a photographic element comprising at least one photo-exposed sllver halideemulsion layer containing an organic, hy-

drophilic, colloid binder comprising hardening said binder by reaction with an aqueous solution of an aldehyde prior to photographic development but-after photoexposure, removing substantially immediately all free aldehyde from said binder prior to any photographic development'by treatment with an aqueous solution of an amine compound selected from the class consisting of (A) a primary amine selected from theclass consisting of hydroxylamine, semicarbazide, hydrazine, 'carbohydraz ide, biuret, aminoguanidine, methylsemicarbaz'ide and watersoluble salts of said compounds and (B) Girards re agent, developing a photographic image by treatment of said silver halide emulsion layer with an aqueous alkaline photographic developer.

2. A process for forming a stable image in a photographic element comprising at least one photo-exposed silver halide emulsion layer containing a water-permeable, organic, hydrophilic, colloid binder comprising hardening said binder by treatment with an aqueous solution of an aldehyde prior to photographic development but after photoexposure, removing substantially immediately all 'free aldehyde from said binder prior to any photographic development by treatment with an aqueous solution of hydroxylamine, and developing a photographic image in said silver halide emulsion layer by treatment of said silver halide emulsion layer with an aqueous alkaline photographic developer.

3. A process for forming a stable image in a photographic element comprising at least one photo-exposed silver halide emulsion layer containing a water-permeable, organic, hydrophilic, colloid binder comprising hardening said binder by treatment with an aqueous solution of an aldehyde prior to photographic development but after photoexposure, removing substantialcompound is carbohydrazine.

ly immediately all'free'aldehyde'from said binder priorto any photographic development by treatment with an aqueous solution of ,carbohydrazide, and developing a photographic image in said silver halide-emulsion layer by treatment of said silver halide emulsion layer with an aqueous alkaline photographic developer.

4. A process for forming a stable image in a photographic element comprising at least one photo-exposed silver halide-emulsion layer'containing' a water-permeable, organic, hydrophilic, colloid. binder comprising hardening said binder by treatment with an aqueous solution of an aldehyde prior to photographic development but after photoexposure, removing substantially rimmediately all free aldehyde from said binder prior to'pany 1 photographicdevelopmenttby treatment'with an aqueous solution of-ser'nic'arbazide, and developing a photographic 7 image in-said silver halide emulsion layer by treatment of said silver halide emulsion layer with an aqueous alkaline photo-graphic developer. a

5. A- process for forming a stable image in a photo graphic element comprising at least one photo-exposed silver halide emulsion layer containing a Water-permeable,

organic, hydrophilic, colloid binder comprising hardening said binder by treatment with an aqueous solution of an aldehydeprior to photographic development butafterphotoexposure, removing substantially immediately all free aldehyde-from said binder-prior to any photographic development by 'treatment'with an aqueous solution of hydrazine, anddeveloping a photographic image in said silver halide emulsion layerby treatment of said silver halide emulsion layer with an aqueous alkaline photographic developenj v 6. A process for forming a'stable image. in a multilayer'photographic element containing a'plurality of 'differentially-sensitized, photo-exposed silver halide emulsion layers containing a water per meabie, organic, hy-

action with an aqueous solution of an'aldehyde prior to photographic development but after. photoexposure,"re-

moving substantially immediately all free aldehyde.- from' 11 In a complete photographic reversal'color-process wherein a'multi-layerphotographic element containing a plurality of ditierentially-sensitized, photo-exposed silver halide emulsion layers' containing a water-permeable, 0r-

ganic, hydrophilic, colloid binder and a color coupler in each-of said layers is' processed in a series of bathsheated to a temperature of at least'85 F. to accelerate processing, the first developing bath being a developing bath for producing a black-and-white negative image, followed by a reversal re-exposureand colordevelopment in a color developing "bath, the steps of hardening the binders of said emulsion-layers by treatmentin'an aqueous aldehyde bathprior to-photographic development but after photoexposure and removing-"of substantially immediately all free aldehyde prior to any photographic"development by treatment of'said'silver halide emulsion layers in an aqueous solution containing an amine compound selected from the class consisting of (A) a primary amine selected from" the class consisting 'o-f"hydroxylamine, semicarbaimmediately all free aldehyde from said colloid binder 7 prior to any photographic development-by treatmentwith an aqueous solution of an amine compound seleete'clfrom drophilic, colloid'binde'r and a color-coupier in ieach of said layers comprising hardening said binder by ;re-

said binder :prior to, any photographic development by treatment with an aqueous solution of an'amine 'jcompound selectedfrom the class consisting of (A) a primary .amine selected from the class consisting of hydroxylamine, semicarbazide, hydrazine, carbohydrazide, biuret,

aminoguanidine, methylsemicarbazide and waterasoluble salts of said compounds and (B) Gira rds reagent, and developing a photographic'ima'ge by treatmentof at least one of said silver halide emulsion layers, with an aqueous alkaline photographic developer.

,7. -A processaccording to claim 6"Wherein said amine compound is-hydroxylamine. i

8. A process according to claim 6 wherein said amine compound is hydrazine; 6 1 '9'. A process, accordingto claim 6 wherein said amine compound is semica'rbazide.

10. A process according to claim 6 wherein said amine "the class consistingof (A) afprimaryamine selected from the class consisting of hydroxylam-in'e, semicarbazide,-hy-

;drazine, 'carbohydraz ide; biuret, aminoguanidine, methylsemicarbazide and Water-soluble salts of said compounds "and (B) Girards reagent.

References (Iited by the Examiner I UNITED STATES PATENTS 4/54' Great Britain; I i OTHER REFERENCES Glafkides: PhotographicChemistry, vol. 1, page 150, Fountain Press, London, 1958/ Weyde et.al' "96946 2,309,492 1/43. Albers a 61. 96-22 XR 2,353,690 I 7/44 Clarkson et'al. 9666 XR 2,675,314 4/54 vermin-.6: a1. -9 6 56 2,984,567"; 5/61 Henn an. 96-22 3,113,864 12/63; Yager at al. 96---22 FOREIGN PATENTS 760,792

NORMANG. TORCHIN, Primary Examiner.

nARoLp NQEURSTEI (deceased)-', Exarhinr. 

1. A PROCESS FOR FORMING A STABLE IMAE IN A PHOTOGRAPHIC ELEMENT COMPRISING AT LEAST ONE PHOTO-EXPOSED SILVER HALIDE EMULSION LAYER CONTAINING AN ORGANIC, HYDROPHILIC, COLLOID BINDER COMPRISING HARDENING SAID BINDER BY REACTION WITH AN AQUEOUS SOLUTION OF AN ALDEHYDE PRIOR T OPHOTOGRAPHIC DEVELOPMENT BUT AFTE PHOTOEXPOSURE, REMOVING SUBSTNATUALLY IMMEDIATELY ALL FREE ALDEHYDE FROM SAID BINDER PRIOR TO ANY PHOTOGRAPHIC DEVELOPMENT BY TREATMENT WITH AN AQUEOUS SOLUTION OF AN AMINE COMPOUND SELECTED FROM THE CLASS CONSISTING OF (A) A PRIMARY AMINE SELECTED FROM THE CLASS CONSISTING OF HYDROXYLAMINE, SEMICARBAZIDE, HYDRAZINE, CARBOHYDRAZIDE, BIURET, AMINOGUANIDINE, AMETHYLSEMICARBAZIDE AND WATERSOLUBLE SALTS OF SAID COMPOUNDS AND (B) GIRARD''S REAGENT, DEVELOPING A PHOTOGRAPHIC IMAGE BY TREATMENT OF SAID SILVER HALIDE EMULSION LAYER WITH AN AQUEOUS ALKALINE PHOTOGRAPHIC DEVELOPER. 